Polymer of a dihydric phenol and an imide

ABSTRACT

A COMPOSITION CONSISTING OF THE REACTION PRODUCT OF A DIHYDRIC PHENOL, A PARTICULAR IMIDE AND A CARBONYL HALIDE WHEREIN THE PARTICULAR IMIDE IS EITHER   2-(X-R-),5-(HOOC-)ISOINDOLINE-1,3-DIONE OR   (5-(HOOC-)ISOINDOLINE-1,3-DION-2-YL)2-R   OR MIXTURES THEREOF. IN THE FORMULAS, R IS DIVALENT HYDROCARBON RADICAL CONTAINING 1 TO 25 CARBON ATOMS AND X IS EITHER A CARBOXYL, A MERCAPTO, A HYDROXYL OR A SECONDARY AMINO GROUP.

United States Patent ABSTRACT OF THE DISCLOSURE A composition consistingof the reaction product of a dihydric phenol, a particular imide and acarbonyl halide wherein the particular imide is either or mixturesthereof. In the formulas, R is divalent hydrocarbon radical containing 1to 25 carbon atoms and X is either a carboxyl, a mercapto, a hydroxyl ora secondary amino group.

HOOC =COOH This invention is a continuation-in-part of US. patentapplication Ser. No. 603,463 filed Dec. 21, 1966, now abandoned.

This invention is directed to particular novel carbonate polymers and inparticular novel copolymers prepared by reacting a dihydric phenol, aparticular imide and a carbonyl halide.

Polycarbonates are a relatively new class of thermoplastics that haverecently become a fast growing commercial product. They are a member ofthe tough thermoplastic family and exhibit excellent properties oftoughness, flexibility, impact resistance, high heat distortiontemperature, etc. These polycarbonates are generally prepared byreaction bisphenol-A and phosgene. However, while the polycarbonatesenjoy many of these excellent properties, they have certain drawbacks inthat they have poor resistance to certain chemicals. In addition, thereis an increasing demand for thermoplastic materials having even higherheat distortion temperatures since there is a demand thereof in areaswhere resistance to high temperatures are needed.

It has been surprisingly discovered taht much greater resistance tocertain chemicals and higher heat resistance can be achieved bypreparing particular carbonate copolymers while the copolymers stillretain the very excellent properties of toughness, flexibility, etc.These copolymers have excellent resistance to such chemicals as carbontetrachloride, gasoline, phosphate esters, etc. and have high heatdistortion temperatures.

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Therefore, it is an object of this invention to provide a particularnovel carbonate copolymer.

These and other objects of this invention will become apparent to oneskilled in the art from the following detailed description thereof.

Briefly, according to this invention, the foregoing and other objectsare attained by reacting a dihydric phenol, a particular imide and acarbonyl halide. The particular imide employed herein is selected fromthe group consisting of:

N-R-X HOOC- ii 0 and N-R-N HO 0 o- -0 0 011 if n O O and mixturesthereof. R in the above formulas is a divalent hydrocarbon radical andcontains 1-25 carbon atoms and is selected from the group consisting ofarylene, alkyl-arylene, aryl-alkylene, cycloalkylene, alkylene andheterocyclic, and X is a mono functional group selected from the groupconsisting of a carboxyl, a mercapto, a hydroxyl and a secondary aminogroup.

The following examples are set forth to illustrate more clearly theprinciple and practice of this invention where parts or percentages arementioned, they are parts or percentages by weight.

EXAMPLE I This example is directed to preparing an imide employed in thepractice of this invention for preparing the novel carbonate copolymer.

One mole of trirnelletic anhydride is reacted with one mole ofp-aminobenzoic acid in dimethyl formamide. The mixture is heated atreflux conditions for about two (2) hours. Water and dimethyl formamideare distilled off. A precipitate is formed and the mixture is cooled toroom temperature. The precipitate is filtered, dried at about C. andrecrystallized from pyridine. The imide so obtained is4-carboxy-N-(4-carboxyphenyl) phthalimide as determined by infraredspectrum analysis and carbon/hydrogen/nitrogen elemental analysis andhas the following chemical configuration:

EXAMPLE II Example I is repeated except that p-aminophenol is employedherein in place of the p-aminobenzoic acid. The resulting imide is4-carboxy-N-(4-hydroxyphenyl) phthalimide as determined by the sameanalyses as employed in Example I and has the following configuration.

EXAMPLE 111 EXAMPLE IV This example is directed to preparing the novelcarbonate copolymer of this invention employing the imide of Example I.

To a reaction flask fitted with a stirrer, a reflux condenser and aphosgene inlet tube, charge 456.6 grams of bisphenol-A (2.0 moles) and3,300 grams of methylene chloride. While stirring, a solution of 63.4grams of the imide of Example I (0.2 mole) in 450 grams of pyridine isthen added, which imide solution is prepared at a temperature of about100 C. Phosgene is then added to the mixture at a rate of about 1.4grams per minute. The end point is reached when the temperature dropsand a heavy viscous solution is obtained. The polymer is precipitatedwith a methanol/hydrochloric acid solution. The polymer is washed, driedand extruded into pellets.

The copolymer prepared herein is identified as Copolymer A.

EXAMPLE V Example IV is repeated except that in place of the imide ofExample I, the imide of Example 11 is employed herein.

The copolymer prepared herein is identified as Copolymer B.

EXAMPLE VI This example is also directed to preparing the novelcarbonate copolymer of this invention employing the imide of ExampleIII.

The imide of Example III is first converted to the acid chloride byreacting the imide with thionyl chloride. To a reaction flask fittedwith a stirrer, reflux condenser, and a phosgene inlet tube, charge203.2 grams (0.89 mole) bisphenol-A and 39.4 grams of the acid chlorideof the imide of Example III (0.067 mole), 2,118 g. methylene chloride,and 230 g. pyridine. Phosgene is then added to the mixture at a rate ofabout 1.4 grams per minute. The end point is reached when thetemperature drops and a heavy viscous solution is obtained. The polymeris precipitated with a methanol/hydrochloric acid solution. Theprecipitate is washed, dried and extruded into pellets.

The copolymer so prepared is identified as Copolymer EMMPL-E VII Thisexample is directed to preparing the novel carbonate copolymer of thisinvention employing the imide of Example I.

To a reaction flask fitted with a stirrer, reflux condenser and phosgeneinlet tube, charge 319.6 grams bisphenol-A (1.4 moles) 171.5 g. (0.56mole) of the imide of Example I and 3,634 g. pyridine. The temperatureis maintained between 70 C. and 100 C. and phosgene is added at a rateof about 1.4 grams per minute. The end point is reached when a heavyviscous solution is obtained. The polymer is precipitated with amethanol/ hydrochloric acid solution. The polymer is washed, dried andextruded into pellets.

The copolymer so prepared is identified as Copolymer EXAMPLE VIII Impactbars, 2 /2" x /2" X Ma" are molded employing the copolymers of ExamplesIV, V, VI and VII. As a control, impact bars molded from a polycarbonateof bisphenol-A and phosgene are prepared and are designated as E. Theimpact bars are then tested for flexural heat distortion in accordancewith AST M Flexural Test D648. The results are as follows:

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Samples: Flexural heat distortion, C. CopolymerA 156.5 Copolymer B 146.5Copolymer C 153.0 Copolymer D 174.0 Copolymer E 132.0

EXAMPLE IX The impact bars as employed in Example VIII are then testedfor chemical resistance employing the single drop test method, whichtest measures the critical elongation in percent strain. Criticalelongation is defined as the maximum flexural strain that can be placedon the impact bar without crazing or cracking when exposed to a givenchemical. The chemicals employed herein are phosphate ester hydraulicfluid (prepared by Monsanto Company). high test gasoline and carbontetrachloride.

polymer system having improved heat distortion and chemical resistance.While polycarbonates of bisphenol-A and phosgene have excellent heatdistortion temperatures when first discovered and disclosed in US.Patent 3,028,- 365, they exhibit poor resistance to certain chemicalmaterials. There is, currently a demand for materials having even higherheat resistance and better chemical resistance. With the instantinvention, it has now been discovered that a particular carbonatepolymer system has much improved chemical resistance and much higherheat distortion temperatures. The results of Examples VIII and IXclearly show that the polymer systems of this invention have a higherheat distortion temperature than a polycarbonate of bisphenol-A andphosgene while exhibiting much improved chemical resistance. Theseadvantages are achieved even with copolymers prepared by reacting minoramounts of the imide with a bisphenol-A.

The novel polymers of this invention consist of the reaction product of(1) a dihydric phenol, (2) a particular imide, and (3) a carbonylhalide. The particular imides employed in the practice of this inventionare those Wherein: selected from the group consisting of:

A B p-Aminothiophenol 4-carboxy-N- -mercaptophenyl) phthalimide.

\ 5 N-phenyl-p-phenylene 4earboxy-N-(4-ani1inophenyl) diamme.phthalimide. p-Aminocinnamlc acid 4-carboxy-N-(4-2 carboxy vinylphenyl)HO O C- phthalirn'de.

G 4-aminocyclol1exan0l 4-carboxy-N-(4-hydroxycyclohexyl) H phthalimide.0 Amlnoacetlc acld 4carb0xy-N-(carboxymethyl) 0 phthalimide. and

0 O The imides employed in place of those in the examples I I and whichproduce essentiall the same results are repared from the reaction ofd1-pr1mary amines with trlmelletic anhydride correspond to the followinggeneral reacti n: Hooo- GOOH o G O [HZNRNH2]A 2IMA II II 0 0 O O y) andmixtures thereof. In the above formula, R is a divalent hydrocarbonradical containing 1-25 carbon atoms and is selected from the groupconsisting of arylene, alkyl- HOOC COOH arylene, arylalkylene,cycloalkylene, alkylene and hetero- O C cyclic radicals. X is a monofunctional group selected from the group consisting of a carboxyl, amercapto, a 0 0 B hydroxyl or a secondary amino group. In the practiceof wh i this invention, several preferred imides are suitable and theseare: A B

Hexamethylenediamine 1,6-bis(4-carboxyphthalimid0)hexane. Ap-Phenylenediamine 1,4-bis(4-carboxyphthalimido)benzene 4,4(l;dia1it(1iinol)fiphenyl 4,4-bls(4-carboxyphthalimido)biphenyl.

enz me 4,4diaminodipheny1 4,4-bis(4-carb0xyphthalimid0) N- 0 0 ether(oxydianiline) diphenyl ether. HO O 4,4diam1nodiphenyl -r4,4-bis(4-carboxyphthalimido) sulfone. diphenyl sulfone.

C Benzoguanamlne 3,5'bis(4-carboxyphenyl) I benzoguanamine.

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The proportion of the monomer that can be reacted can or vary dependingupon the end use application of the co- 0 polymer and the propertiesdesired. Preferably, the proportions vary from about 9.9-6.0 moles andparticularly 9.5-8.5 moles of the dihydric phenol, and correspondingly,about 0.4-4.0 moles and particularly 0.5-1.5 moles of the particularimide. HOOOT The dihydric phenols that can be employed in the practiceof this invention are any of the well known dihydric phenols.Preferably, the dihydric phenols employed in the 5 practice of thisinvention can be those compounds dis- The Hulda? employed 111 thepractlcepf thls lPventloP closed in US. Patents 3,028,365, 2,999,835,3,030,331 and are those imides prepared by the reactlon oi trlm3,169,121, all of which are hereby incorporated by referanhylnde Wlthammes contammg a mono ence. The dihydric phenols which can be employedin functlonal group WhlCh 1s either a carboxyl, a mercapto, place of thebisphenol A (2,2433(4 hydroxyphenyl) a hydroxyl or a se c ndary ammogroup. A lncluded pane) used in the examples to prepare the carbonateherein F those f g q by 2 moles of polymers are mononuclear orpolynuclear aromatic comtfimelletlc anhydnde Wlth a dlpnmary f poundscontaining as functional groups, two hydroxy radi- The imides employedin Place of those m the examples cals, each of which is attacheddirectly to a carbon atom and which produce essentially the same resultsare pref an aromatic nucleus and are, f Example, 2,221,344- pared fromthe react o of -P y amines with hydroxy-3-methylphenyl)propane, 1,1-bis(4 hydroxytrimelletic anhydride correspond to the following generalphenyl) cyclohexane, 4,4'-dihydroxydiphenyl 4 reaction: droxydiphenylsulfone, 4,4-dihydroXydiphenyl ether, 2,6-

0 dihydroxynaphthalene and 1,1-bis-(4-hydroxyphenyl) 2,2, lZ-trichloroethane. In the practice of this invention, it is, of course,possible to employ two or more difierent dihydric phenols or a copolymerof a dihydric phenol with HO O a glycol, a hydroxy or an acid-terminatedpolyester, or a dibasic acid in the event a carbonate copolymer ratherthan a homopolymer is desired for use in the preparation 0 B of thenovel carbonate polymers of this invention.

The carbonyl halide employed in the practice of this and mixturesthereof, wherein R is a divalent hydrocarbon invention can be carbonylchloride, carbonyl bromide or radical containing 1-25 carbon atoms andis selected from carbonyl fluoride. Preferably, the carbonyl halideemployed the group consisting of arylene, alkyl-arylene,aryl-alkylherein is phosgene, a carbonyl chloride. ene, cycloalkyleneand alkylene radicals and X is a mono It will thus be seen that theobjects set forth above, 5 functional group selected from the groupconsisting of a among those made apparent from the precedingdescripcarboxyl, a mercapto, a hydroxyl and anilino, and (3) a tion areefiiciently attained, and since certain changes may carbonyl halide. bemade in carrying out the above process and the com- 2. The compositionof claim 1 wherein the polymer is position set forth without departingfrom the scope of the the reaction product of 9.5-8.5 moles of thedihydric invention, it is intended that all matters contained in thephenol and, correspondingly, 0.5-1.5 moles of the imide.

above description shall be interpreted as illustrative and 3. Thecomposition of claim 1 wherein the dihydric not in a limiting sense.phenol is 2,2-bis-(4-hydroxyphenyl)-propane.

What is claimed is: 4. The composition of claim 1 wherein the imideis: 1. A polymer consisting of the reaction product of (1) 9.9-6.0 molesof a dihydric phenol, (2) 0.4-4.0 moles of 0 an imide selected from thegroup consisting of: 4

o g N@COOH nooo- N-R-X f noooo c 5. The composition of claim 1 whereinthe imide is:

0 ll ll N/ Mm Hooo- CO0H o o 1% II 0 and References Cited UNITED STATESPATENTS 0 0 3,205,199 9/1965 Preston et a1 26047 l 3,320,211 5/1967Bissinger et al 26047 3,399,172 8/1968 Jaquiss 26047 N-R-N HOOC COOHSAMUEL H. BLECH, Primary Examiner f E, US. 01. X.R. 0 0 260326 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 7,6 5 DatedMarch 2, 1971 Inventor(s) C. A. Bialous and M. L. Evans It is certifiedthat error appears in the above-identified pater and that said LettersPatent are hereby corrected as shown below:

In the Abstract, column 1, line 23, the left-hand part the formulashould appear as follows:

HOOC== should read HOQC- In the Abstract, column 1, line 32, the farleft-hand 4 far right-hand parts of the formula should appear as follow:

HOOC- =COOH should read HOOC- -COOH In column 1, line 62 "taht" shouldbe -that--.

Signed and sealed this 11th day of January 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer ActingCommissioner of Pa

